Production of monohaloalkanes



Patented Dec. 5, 1950 2,533,053 PRODUCTION or MONOHALOALKANES Louis Schmerling', Riverside, Ill., assignor to Universal Gil Products Company, Chicago, 111., a

corporation of Delaware No Drawing. Application September 28, 1946, Serial No. 700,176

17 Claims.

This application is a continuation-in-part of my cope-nding app'icatons Serial Numbers 551,- 262 now abandoned, and 551,263 now abandoned, each filed August 25, 1944, and application Serial Number 600,216, now abandoned, filed June 18, 1945, each of which is a continuation in-part of my application Serial Number 438,841, now abandoned, filed April 13, 1942.

This invention relates to the production of monohaloalkanes in which the halogen has an atomic weight of at least 35. More particularly, the process relates to the addition of a particular monoolefin to a monohaloakane' having at least three carbon atoms per molecule to produce a higher boiling monohaloalkane with a molecular weight equal to the sum of the molecular weights of the monoolefin and monohaloalkane charged to the process. I

The process is concerned with a catalytic method of adding to a monoolefin or condensing therewith a monoch1oro, monobromo-' or monoiodoalkane having at least three carbon atoms per molecule. v

In this specificaton the term condensing is used in referring to the process of chemically combining a monohaloalkane with at least three carbon atoms per molecule in which the halogenhas an atomic weight of at least 35 with a monoolefin having at least one hydrogen atom com bined with each of the carbon atoms joined by A further object of this invention is to provide a process for condensinga non-tert-monoolefin and a monohaloalkane in which the halogen had an atomic weight of at least 35 in the presence of a Friedel-Crafts metal halide catalyst.

One specific embodiment of the present invention comprises the process for producing a higher boiling monochloroalkane by condensing a lower boiling monohaloalkane and a mono-olefin having at least one hydrogen atom combined with each of the carbon atoms joined by the double bond, in the presence of a catalyst com-prising as" its essential active ingredient a Frieda-Crafts metal halide.

Another embodiment of this invention coniprises a process for producing a higher boiling monobromoalkane by condensing a lower boiling monobromoalkane and a monoolefin having at least one hydrogen atom combined with each of the carbon atoms joined by the double bond at a my process contain at least three carbon atoms and only one halogen atom per molecule, this halogen havingan atomic weight of at least 35- and thus being a member of the group consiste ing of chlorine, bromine, and iodine.

I- ha'v'e found that the monohalo'all anes having less than three carbon atoms per molecule,- namely, the methyl and ethyl halides, do not add to or condense with olefins as aforementioned to produce higher boling monol'ialoa'lkanes in the presence of a FriedeleCra'fts catalyst but that suic'h a reaction mixture yields olefin polymers as the principal product of the process.

The different monohaloalkanes which are usable in my process are usua 1y referred to as primary, secondary, and tertiary alkyl halides or nionohalo'alkanes and may be represented by the following structural formulae wherein each of R R and R represents a member of the group consisting of a hydrogen atom and an alkyl group and X represents a halogen atom with an atomic weight of at least 35.

Tertiary An p atic mon clefi h d ocarbon ich is condensed with a monohalo l an ill-m p ose i i I t -.C=T C.R

in' which each of R and R represents memeber of the group consisting of a hydrogen atom and an alkyl group; The monoo leiin is a primary inonooleiin when at least one of R and It represents a hydrogen atom. The mcnoolefin is a secondary monoolefin when R and R represent alkyl groups.

The rnonoolefins generally referred to as primary, secondary, and tertiary monoolefins have the following structural formula in which R and R represent alkyl groups:

A tertiary moncolefin which is a monoolefin in which there is no hydrogen atom combined with one of the carbon atoms joined by a double bond to another carbon atom sometimes has more of a tendency to polymerize than to add or condense with a monohaloalkane although the addition reaction may occur to a certain extent when tertiary alkyl halides are used. However, there is little utility in effecting the condensation of a tertiary alkyl chloride with a tertiary olefin since the same product can be obtained in better yield by polymerizing the olefin and then adding hydrogen chloride to the dimer.

Catalysts employed in my condensation process comprise Friedel-Crafts metal halides and particularly anhydrous aluminum chloride, aluminum bromide, ferric chloride, zirconium chloride, zinc chloride, bismuth chloride, stamiic chloride, titanium tetrachloride, etc. These different catalytic materials may be used as such or they may be composi'ted with one another or be deposited upon solid carriers or supporting materials to produce catalyst composited of desired activities. Suitable catalyst carriers or supports include both absorptive and substantially non-absorptive materials such as alumina, activated charcoal, crushed porcelain, diatomaceous earth, pumice, firebrick, etc. The carrier should be substantially inert in the sense that substantially no interaction which is detrimental to the activity or selectivity of the catalyst composite occurs between the carrier and metal halide.

In some cases, the catalyst may be employed in the form of a solution in a solvent such as a nitroparafiin or an ether. Solutions of this type are readily commingled with the reacting monohaloalkane and monoolefinic hydrocarbon. Obviously, the solvent chosen should be one which does not itself undergo undesirable reaction under the operating conditions utilized.

Sometimes it may be advisable also to mix with the reacting alkyl halide and olefin, a small amount of a peroxide, for example ascaridole, benzoyl peroxide, etc., to influence the manner in which an alkyl halide condenses with an olefin to produce higher boiling alkyl halides of desired structures.

Previous to my work, no condensation of monohaloalkanes with monoolefinic hydrocarbons in the presence of a metal halide catalyst of the Friedel-Crafts type has been reported. It was known, however, that a polyhaloalkane would condense with a haloolefin in the presence of the aluminum chloride catalyst. Thus chloroform and/or carbon tetrachloride were condensed previously with di-, tri-, and tetrachloroethylene, in the presence of an aluminum chloride catalyst. Later, other workers disclosed the condensation of 1,1-dichloroethane with a chloroethylene.

Theoretical reasons were given by one investigator to show that it would not be possible to condense a monohaloalkane with a monoolefin or even with a haloolefin. It was stated that a haloalkane requires strong activation and reacts only when its molecules are polarized by the presence of a plurality of halogen atoms, in other words, the haloalkane must be a polyhaloalkane. It is to be noted that in all of the prior art examples the saturated halide (as a haloalkane) contained at least two halogen atoms combined with a single carbon atom. It is to be emphasized, too, that it was found by the prior art workers, and verified by myself, that even such polyhalides (that is, chloroform and carbon tetrachloride) can not be condensed with a monoolefin (that is, a non-halogenated unsaturated compound) in th the presence of aluminum chloride. Thus it is seen that previous to my discovery, neither monohalo or polyhalo saturated hydrocarbons had been condensed with olefinic hydrocarbons.

The polyhalogenated saturated hydrocarbons used in the prior art undergo little or no change when heated with aluminum chloride at the condensation conditions but in the absence of a haloolefin. Thus a prior art investigator refluxed chloroform and dichloroethylene separately with aluminum chloride and obtained little change in either reactant. He then mixed the chloroform and dichloroethylene and heated the mixture with aluminum chloride at 50 C. and effected condensation to pentachloropropane. It is important to note that chloroform itself did not react when heated with the aluminum chloride catalyst. In contrast with these results, if a monohaloparafiln such as that used in the process of my invention is contacted with aluminum chloride, even at room temperature, a vigorous reaction occurs, and hydrogen chloride is evolved.

Another important difference between the process of my invention and the prior art is the fact that my process can be carried out in the presence of many catalysts of the Friedel- Crafts type ranging in activities from such feebly active substances as mercuric chloride and moderately active substances as bismuth chloride to very active catalysts such as ferric chloride and aluminum chloride, whereas the prior art shows that only aluminum chloride can be used as catalyst for the condensation of a polyhaloalkane with a haloolefin; attempts by the earlier workers as well as by the present applicant have shown that even ferric chloride can not be used in place of aluminum chloride in the condensation of a polyhaloalkane and a haloolefin.

A further statement concerning the prior art on the condensation of a haloalkane and a monoolefin or haloolefin was given by C. A. Thomas (Anhydrous Aluminum Chloride in Organic Chemistry, Reinhold Publishing Corporation, 1941, page 777) as follows:

The addition of chlorinated parafiins to olefinic chlorides in the presence of aluminum chloride is not of general applicability. (H. J. Prins, Rec. trav. chim. 51, 1065-1080 (1932); Chemical Abstracts 27, 489.) Monoand dichloromethane have been found to give no reaction. With the olefins, the reaction velocity was found to in crease from tetrachloroto monochloroethylene. Ethylene, itself, however, did not enter into the reaction, even with highly activated chloro-compounds. Certain chloroethanes can also add to chloroethylenes, the reaction velocity, however, being slower than that with the chloromethanes. Chloropropanes do not react with chloroethylenes, except pentachloropropane.

acesee The foregoing statement of Thomas thu shows that even more than years after the original discovery of the Prins reaction, it was not known that alkyl halides containing at least three carbon atoms could be condensed with olefins;

My process also differs from that of another reference of the prior art which discloses the condensation of a monohaloalkane with poly olefinicsubstance which must contain at least two double bonds per molecule.

The present process for reacting a monolefin and a monohaloalkane having at least 3 carbon atoms per molecule in which the halogen ha an atomic weight of at least apparently involves the addition of the monaholalkane to the double bond of the monolefinic hydrocarbon so as to produce another monohaloalkane of higher molecularweight. For example, the condensation of 1-chloro-z-methyl-propane with ethylene produces 1-chloro 3,3-dimethylbutane which is a primary hexyl chloride, as illustrated by the following equation:

n-Propyl chloride and n-butyl chloride each react with two molecules of ethylene to yield 1- chloro 3,3 dimethylpentane and 1 chloro-3- methyl-B-ethylpentane, respectively.

CH5 omon omoi 2cH2=CH2 OHaCHzJ-CHzGHaCl CHgCHzCHzCHzCl 2ong=cng om CH3GH2( 3OE*I2CH2Gl The condensation of a secondary monohaloalkane with a monoolefin is illustrated by the in teraction of 2-chlorobutane with ethylene to produce l-chloro-3-methylpentane as illustrated by the following equation:

C a'C-C 'rC s 2043 2 c sCHeQ-CfizCHzCl Cl (EH3 At the reaction conditions, the hexyl chloride thus formed may react with a second molecule of ethylene to yield l-chloro-3-inethyl-3-ethylpentane which is usually obtained as the chief product or the reaction of 2-chlorobutane with ethylene:

'2-I l'alobutanes undergo similar condensations with propylene and with butylenes producing halohe'pta'nes and halooctanes, respectively, as the primary products. In some cases, the prod use thus formed is more reactive than is the orig- "2-halobu'tan'e and may react with a second and then a third, etc., molecule of the olefin.

The addition of tertiary butyl chloride, which may also be referred to as 2chloro-2-methylpropane, to ethylene produces i-chloro-3,3-dimethylbut'a'n'e which is also 'a chloroneohexane. This 6 condensation reaction to produce chloroneohex ane is illustrated by the following equation:

The 1-chloro-3,3-dimethylbutane is the principal product of this condensation reaction and no isomeric chlorohexanes are observed in the reaction products. A by-product of this reaction, particularly when using ferric chloride catalyst, is l-chloro-3,3-dimethylpentane.

I A similar reaction between tertiary amyl chloride and ethylene in the presence of aluminum chloride at about 5 C, yielded 25% of l-chloro- 3,3-di-methylpentane, and 12% of 1-chloro-3,3- dimethylbutane.

2-chloro-2-methylpropane underwent similar condensations with propylene and with n-butylenes to produce chloro-heptane and chloro-o'ctance, respectively. Similarly, as illustrated by the following equation, a bromoheptane was obtainable by the reaction of 2-bromo-2-rriethylpropane with propylene.

The condensations of different monohaloalkanes with different olefins are not necessarily effected with equal efiiciencies or under the same conditions of operation. Further, the reaction temperature depends also on the catalyst used. Thus in the presence of an aluminum chloride catalyst, a temperature of from about -30 to about 10 C. is utilized generally when condensing a monohaloalkane with a primary or secondary monoolefin. When employing a less active catalyst such as bismuth chloride, a temperature of from about 0 C. to about 50 C. is preferable for condensing a tertiary alkyl chloride, bromide, or iodide, with an olefin containing at least three carbon atoms per molecule while a. temperature of from about 25 to about C. is employed in condensing these olefins with primary and secondary monohaloalkanes and a temperature of about 50 to about C. is suitable for sim ilar reaction between tertiary butyl chloride and ethylene. A temperature of from about 0 C. to about 50 C. is suitable for condensing ethylene, propylene, butylenes, and higher olefins with alkyl chlorides and bromides such as n-propyl chloride, isopropyl chloride, isobutyl chloride, tertiary butyl bromide, etc., in the presence of ferric chloride or zirconium chloride. Other Friedel-Crafts type metal halides also require rather narrow ranges of temperature for catalyzing the production of high yields of higher boiling haloalkanes in which the halogen has an atomic weight of at least 35.

The reaction of a monohaloalkane with a monoolefin in the presence of a catalyst is carried out using either batch or continuous operation. A hydrogen halide as hydrogen chloride, hydrogen bromide, or hydrogen iodide may also be introduced with the olefin and monohaloalkane charged. In batch type operations, desired proportions of lower boiling monohaloalkane and clefin or of mo-nohaloalkane and a hydrocarbon fraction containing monoolefinic hydrocarbons? are introduced to a suitable reactor containing the 7 FriedeLCrafts type catalyst as such or composited with a carrier or in solution in a suitable solvent, and the resultant commingled materials are contacted until substantial proportions of the reactants are converted into the desired higher molecular weight haloalkanes. The reaction mixture, after separation from the catalyst is fractionated to separate the unconverted monoolefini'c hydrocarbon fraction and the unconverted monohaloalkane from the higher boiling mono haloalkane produced. The recovered monoolefinic hydrocarbon fraction and lower boiling monohaloalkane may be used in another run.

Continuous operations may be carried out by directing a mixture of a monoolefinic hydrocarbon and a monohaloalkane through a reactor of suitable design containing a bed of catalyst of the Friedel-Crafts type. In this type of treatment, the operating conditions may be adjusted suitably, and these may difier somewhat from those used in batch type operations. Thus, when a mixture of a monohaloalkane and an olefin was passed, for example, through a tube containing ferric chloride supported by granular porcelain, the formation of the desired higher boiling monohaloalkane was effected by using a higher temperature and shorter time of contact than those used when contacting a similar reaction mixture and catalyst at a lower temperature and in a batch type reactor, such as an autoclave provided with suitable stirring means.

By the process of this invention, I have prepared a number of novel secondary monohalooctanes (also called secondary octyl halides) containing a quaternary carbon atom. Thus the condensation of tertiary butyl chloride and l-butylene produced 3-chloro-5,5-di1nethylhexane, while the condensation of tertiary butyl chloride and Z-butylene yielded 2-chloro-3,4,4-trimethylpentane. I have also condensed tertiary amyl chloride and 2-butylene to produce z chloro-3A/itrimethylhexane. Reaction of tertiary amyl bromide with Z-butylene by my process has similarly yielded 2-brorno-3,4,4.-trimethylhexane which is a mono-bromononane containing a quaternary carbon atom.

The products of my process, namely, the different higher boiling monohaloalkanes such as monochlorohexanes, -heptanes, -octanes, and other monohalohydrocarbons may be used for various purposes. For example, they may be converted into hydrocarbons or high antiknocl: value, or they may be utilized as solvents or as intermediates in organic syntheses. This process thus serves as a means for transforming normally gaseous monoolefins such as ethylene, propylene, and the n-butylenes, as well as relatively low boiling normally liquid primary and secondary olefins, such as various isomeric pentenes, hexenes, etc., into monohaloalkanes of higher molecular weight, the latter being then convertible into olefinic or parafiinic hydrocarbons with highly branched chain structures and utilizable in the production of aviation gasoline. The reaction of the various types of alkyl halides with ethylene has the further advantage that it yields higher molecular weight primary halides which are of particular value and desirability for certain processes; e. g. conversion to nitriles and to alkylsulionates by reaction with metal cyanides and metal sulfites, respectively.

The following examples are given to illustrate the character of the results obtained by the use of the specific embodiment of the present process, although the data presented are not introduced with the intention of restricting unduly the generally broad scope of the invention.

EXAIVIPLE I 12 grams of ethylene was passed into a stirred mixture of '75 grams of normal propyl chloride and 6 grams of anhydrous aluminum chloride during a period of 1.5 hours while the reaction mixture was maintained at a temperature of from 2 to 6 C. and at atmospheric pressure. The reaction product so obtained consisted of about 1 gram of catalyst layer and 83 grams of liquid product containing about 6 grams of catalyst in solution. Investigation of the liquid product showed that a 25% yield of 1-chloro-3,3-dimethylpentane was obtained based. upon the ethylene which reacted.

EXAMPLE II 10 grams of ethylene was added with stirring during a period of 1 hour to a mixture of 50 grams of isobutyl chloride, 50 grams of n-pentane diluent, and 5 grams of aluminum chloride maintained at a temperature between 25 and 10 C. The reaction product so obtained consisted of 11 grams of catalyst layer, 1 gram of hydrogen chloride, and 103 grams of a liquid product. 1- chloro-SB-dimethylbutane was present in the liquid product in an amount equivalent to 40% of the theoretical yield based upon the isobutyl chloride charged or in about a 60% yield based upon the ethylene absorbed in the reaction.

EXAlVIPLE III 26 grams of ethylene was added with stirring during a period of 0.5 hour to a reaction mixture cont-l sling 51 grams of n-butyl chloride, 50 grams of pentane diluent, and 10 grams of anhydrous aluminum chloride maintained at a temperature of from -20 to 0 C. The reaction product consisted of 16 grams of catalyst, 1 gram of hydrogen chloride, and 114 grams of liquid product. This liquid product contained l-chloro-3-methyl-3- ethylpentane in amount equivalent to 15% of the.

theoretical yield, based upon the n-butyl chloride which reacted.

EXAMPLE IV 16 grams of ethylene was introduced with stirring at atmospheric pressure during a period of 0.6 hour to a reactor containing 50 grams of isopropyl chloride, 50 grams of n-pentane diluent, and 5 grams of anhydrous aluminum chloride maintained at a temperature of from 18 to 14 C. The reaction product consisted of 6 grams of a catalyst layer and 115 grams of liquid product. The liquid product contained 20 grams of 1-chloro-3,3-dimethylpentane boiling mainly at bis-149 C. and having an index of refraction, n of 1.4261. The recovered liquid product also contained cc. of a mixture of isopropyl chloride and pentane and 8 grams of liquid boiling higher than 1-chloro-3,3-dimethylpentane.

pheres.

EXAMPLE VI 58 grams of isopropyl chloride and grams of ferric chloride were placed ina glass-lined autoclave to which ethylene was charged to 40 atmospheres pressure after which the charged autoclave was rotated for 4 hours at 24 C. and then allowed to stand for 15 hours after which time the pressure reached 28 atmospheres. After releasing the excess of ethylene, a reaction product was removed from the autoclave consisting of 62 grams of liquid and 5 grams of catalyst, each brown in color. The liquid product was separated by distillation into the following fractions: 78% by volume boiling below 40 C. and consisting essentially of unconverted isopropyl chloride, 1% by volume boiling between 100 and 125 C., 14% boiling between 125 and 150 C. and 6% of higher boiling material. The fraction boiling between 125 and 150 C. contained 8 grams of l-chloro- 3,3-dimethylpentane, an amount equivalent to an 8% yield based upon the isopropyl chloride charged or 20% based on the isopropyl chloride which reacted.

EXAMPLE VII The autoclave used in Example VI was charged similarly with 40 grams of isopropyl chloride, and

10 grams of bismuth chloride. Ethylene was then introduced to an initial pressure of 40 atmospheres and the autoclave was rotated while its temperature was increased and maintained at 100 C. for a period of 4 hours. After, the autoclave had cooled to room temperature, the final pressure of the reaction mixture was 27 atmos- The reaction mixture which was obtained consisted of 3'? grams of liquid product,

14 grams of a reddish-brown tar containing'the catalyst and 5 grams of gaseous products condensable at 78 C. Besides containing 27 grams of isopropyl chloride, the recovered liquid product consisted of 4 cc. boiling between 40 and '100" C., 5 cc. boiling from 100 to 125 C., 12 cc.

boiling between 125 and 150 C., and 15 cc. of higher boiling liquids. The yield of 'l-chloro- 3,3- dimethylpentane was 18% of the theoretical based on the unrecovered isopropyl chloride.

EXAMPLE VIII 26 grams of ethylene was introduced at atmospheric pressure during 0.5 hour to a stirred reaction mixture consisting of 50 grams of secondary butyl chloride, 50 grams of n-pentane diluent, and 5 grams of aluminum chloride maintained at a temperature of from -16 to 10 C.

The reaction product obtained consisted of 123 EXAMPLE IX Using the same method of procedure as described in Example VIII, ethylene was passed at atmospheric pressure. during a period of 1.8 hours into a stirred mixture of 100 grams of secondary butyl bromide, 53 grams of n-pentane diluent, and 8 grams of aluminium chloride, the temperature of the reaction mixture being maintained between -22 and -18 C. by a cooling bath surrounding the reactor. During the reaction, there was a 51 gram increase in weight of the reaction mixture due to the ethylene reacting and dissolving therein. The reaction product.

obtained consisted of 26 grams of a yellow catalyst sludge and 186 grams of liquid, the latter being then washedfdried, and distilled. Distillation of the dried liquid products separated therefrom 45 grams of bromo-octane boiling chiefly at 40-42 C. at a pressure of 3 mm. of mercury having an index of refraction, n of 1.456, and a specific gravity, (14 of 1.11. The bromo-cctane was identified as chiefly l-bromo- 3-methyl-3-ethylpentane.

EXAMPLE X 120 grams of tertiary butyl chloride and 1'? grams of bismuth chloride were placed in a glass liner which was then enclosed in a rotatable autoclave to which ethylene was added to a pressure of 40 atmospheres. The temperature of the autoclave was then raised and maintained at the operating temperature of C. and the autoclave was rotated for 4 hours. The pressure reached a maximum of 48 atmospheres, decreased to 38 atmospheres at the end of 1 hour, and reached a final pressure of 5 atmospheres after the autoclave cooled to room temperature. The reaction products removed from the autoclave consisted of 131 grams of colorless liquid and 22 grams of a reddish-brown catalyst sludge or tar. The liquid product was washed with caustic and water, then dried and fractionally distilled beginning at ordinary pressure, and gradually reducing the pressure as the boiling point of the product increased. The different fractions so obtained had the properties shown in Table 1.

Table 1.Dz'stillation of products formed by condensation of tertiarybutyl chloride with ethylene in the presence of bismuth chloride B. P. B. P. Pressure Vol Fraction No. C. at m 760 mm.

Fractions l-3, inclusive, consisted mainly of unconverted tertiary butyl chloride and fraction 4 was an intermediate fraction. Fraction 5, which on redistillation boiled at 116-117 C. at 740 mm. pressure had a density of 0.8670 at 20 C. and a molecular weight of 113 as determined cyroscopically. This molecular weight thus corresponded to that of a hexyl chloride. By means of a Grignard reagent the hexyl chloride was converted into the corresponding alcohol, and the latter yielded an alpha-naphthylurethan melting at 81-82 C., a 3,5-dinitro-benzoate melting at 81-82" C., and an alpha-naphthylamine addition compound of the, dinitrobenzoate melting at l32-133 C. These derivatives prove that the alcohol was 3,3-dimethyl butanol-l and accordingly that the chloro compound was 1-chloro-3,3-dimethylbutane, that is a chloroneohexane. The compound 1- bromo-3,3-dimethyl butane was obtained similarly from the condensation of tertiary butyl bromide with ethylene. Each of these halo genated neohexanes may be referred to as a 1- halo-3,3-dimethyl butane.

Theresidue indicated in Table 1 apparently contained higher boiling haloalkanes probably 1 1 formed by condensation of chloroneohexane with ethylene.

EXAMPLE XI In another run, carried out similarly to that described in Example X, 54 grams of tertiary butyl chloride and 5 grams of anhydrous ferric chloride were charged to the autoclave to which ethylene was then added to 40 atmospheres pressure. While the autoclave was then rotated at room temperature, the pressure dropped to 30 atmospheres at the end of two hours. After the autoclave had been rotated for 4 hours, the rotating was stopped and the autoclave was allowed to stand at room temperature for 6"! hours, at the end of which time the pressure was 18 atmospheres. From the reaction product was separated 6'? grams of a reddish-brown liquid and 8 grams of catalyst in the form of brown lumps. The liquid product was washed with water, dried, and distilled into the fractions shown in Table 2.

Table 2.Distillation of product formed by condensation of tertiary butyl chloride with ethylene in the presence of ferric chloride Fraction 2 consisted of 1-chloro-3,3-dimethylbutane which was identified as mentioned in Example X.

EXAMPLE XII This run was carried out in a manenr similar to that shown in Example X except that 75 grams of liquefied propylene was weighed into a glass autoclave-liner, previously cooled to 78 C. and containing 140 grams of tertiary butyl chloride and 10 grams of bismuth chloride. After the autoclave-liner containing the reaction mixture was placed in the autoclave, the latter was closed, and nitrogen was added to a total pressure of 50 atmospheres. The charged autoclave was then rotated at 20 C. for 4 hours after which the rotation was stopped and the autoclave allowed to stand at 20 C. for 16 hours. The resultant reaction product consisted of 35 grams of unconverted propylene, 1'73 grams of liquid containing some dissolved propylene, and 12 grams of catalyst in the form of white lumps. After washing and drying, the total of 165 cc. of liquid product was distilled into the fractions shown in Table 3.

Table 3.Distillation of product formed by condensation of tertiary butyl chloride with propylene in the presence of bismuth chloride Fraction 5 had a density of 0.8691 at 20 C. and a molecular weight of 129 as determined cryoscopically in benzene. A portion of fraction 5 was converted into the corresponding al- 5 cohol which yielded a 3,5-dinitrobenzoate melting at 94.5-95.5 C. and an alpha naphthylurethan melting at 86-87 C. thus proving that fraction 5 was 2-chloro-4,4-dimethylpentane.

1O EXAMPLE XHI Zirconium chloride was also employed as catalyst for the condensation of tertiary butyl chloride with propylene under the same conditions as shown in Example XII, employing a reaction mixture of 50 grams of tertiary butyl chloride, 21 grams of propylene, and 10 grams of Zirconium chloride. The reaction product yielded approximately 10 grams of chloroheptane boiling between 127 and 136 C.

EXAMPLE IHV Table 4.Distillation of product formed by condensation of tertiary butyl chloride with nbutylenes in the presence 0 bismuth chloride B. P., C. at 760 mm.

Pressure. mm.

Vol.,

EXAMPLE XV 0 72 grams of tertiary butyl bromide, 32 grams of propylene, 0.1 gram of ascaridole, and 3 grams of bismuth chloride were placed in an autoclave to which nitrogen was added to a pressure of 50 atmospheres after which the autoclave was rotated for 4 hours at 25 C. The autoclave and contents then stood for 16 hours. The reaction products removed from the autoclave consisted of 98 grams of pale yellow liquid free from hydrogen bromide and 5 grams of used catalyst, the latter being orange in color. During the reaction the propylene underwent complete conversion. The pale yellow liquid was dissolved in pentane to facilitate washing with caustic and water after which the pentane solution was dried and fractionally distilled to give (after removal of pentane) 12 EXAMPLE XVI In a number of runs, ethylene was passed at atmospheric pressure into a stirred mixture of a monohaloalkane, aluminum chloride, and in some instances, n-pentane, the latter employed as a solvent or diluent. These runs were carried out in a 3-necked flask equipped with an inlet tube for ethylene, a mercury-sealed stirrer, and a reflux condenser. The monohaloalkane and npentane, when the latter was used, were placed in the flask and then cooled to about -60 C. by immersion in a cooling bath. The catalyst was added, the cooling bath was removed from around the reaction flask, and ethylene was passed into the well-stirred mixture by means of a tube, dipping below the surface of the reaction mixture. The temperature of the reaction mixture was permitted to rise until absorption of ethylene began, this being determined by a difference in the rates of bubbling through inlet and exit bubblers. The reaction temperature was then maintained at about that needed for ethylene absorption either until the desired amount of ethylene was absorbed as indicated by increase in weight, or until absorption of ethylene ceased. The reaction mixture was then cooled to about 40 C., the liquid was decanted from the catalyst and the liquid was washed, dried, and distilled at reduced pressure.

By using this procedure, ethylene, and the monohaloalkanes listed in Table were condensed in The above indicated condensation involving tertiary butyl chloride and ethylene yielded 1- chloro-3,3-dimethylbutane as the principal prodnot. The similar condensation of tertiary amyl chloride and ethylene, and of tertiary amyl bromide and ethylene in the presence of aluminum chloride yielded, respectively, l-chloro-, and lbromo-3,3-dimethylpentanes.. The condensation reaction between tertiary amyl bromide and ethylene also gave a nonyl bromide in substantial yield. 1-chloro-3,3-dimethy1butane was a byproduct of the reaction of t-amyl chloride with ethylene.

EXAMPLE XVII Other runs were made using essentially the apparatus and procedure employed in Examples X to XV, inclusive. A monohaloalkane was weighed into an autoclave liner made of glass, the liner and monohaloalkane were cooled to -78 0., the catalyst was added thereto, and the liner was sealed into a rotatable steel autoclave of 850 cc. capacity. The sealed autoclave was then charged with ethylene to about -50 atmospheres pressure. The autoclave was rotated at the desired temperature for 4 hours, more ethylene was added if the pressure fell below 25 atmospheres, the autoclave was allowed to stand overnight, then opened, and the product worked up as described in the preceding example.

In these runs, the monohaloalkanes listed in Table 6 were condensed with ethylene in the presence of the catalysts and at the temperatures shown in the table. In these runs, no attempt was made to determine the amount of ethylene which reacted.

Table 6.Condensatio'n of tertiary butyl and tertiary amyl halides with ethylene at superatmospheric pressure in the presen cc of a Friedel-Crafts type metal halide Alkyl Halide Main Product Yield Run No. MX grams i g" RX grams RX Percent grams of RX Charged BiCla- 1O 50 4 6 5O c... 10 l-chloro-3,3 diI ethy1-butane... 2O 30 23 2 22 i 14 6 3... 2 28 13( g? 3 g }l-bromo-3,3-d1methylbutane g 23 Fe a. 0 0 25 100 mom" 10 50 }1-bromo-3.3vd1mcthylpentancuh, 14 12 the presence of the cata ysts and at the temperatures also shown in the table.

The above-described reactions of tertiary butyl chloride with ethylene yielded 1-chloro-3,3di-

Table 5.C07Ld e'nsati0n of ethylene with tertiary alkyl halides at atmospheric pressure in the presence of aluminum chloride Alkyl halide, RX Main Product Yield Run C2114, A1013, grams .grams rlemp" RX Grams RX Percent Grams of RX c arge tert-C4HnOl 1 50 20 3 15 to 10 l-chloro-3,3-diinethy1butane. 49 75 tert-O fiuCl l8 l5 l() to '2 lPch1oro-3,3-dimethylpentane. 2 48 25 tert-C5H1 Br.. 1 102 35 3 23 to -17 1-brom0 3,3-d methylpentcne 48 40 CeHmBr 3O 2O 1 Also n-pentane (50 g.) was used as diluent. 7 There was also obtained as byproduct, 2U l-chloro-S,B-dimethylbutane.

g. (12% of the theoretical yield based on the amyl chloride charged) of 3 Boiling point. 51-52 0., at 10 mm. or l67-l68 C. at 760 mm. pressure; 7m, 1.45 16; d4. 1.1497. 4 BDlllIlg mm, 60-61 C. at 3 or 205205 Q. at 760 mmpressure; up, 1.4530; at", 1.0950,

15 methylbutane as the principal product. No evidence of the formation of isomeric chlorohexanes was obtained. A by-product of the reaction, particularly when it was catalyzed by ferric chloride, was 1-chloro-3,3-dimethylpentane.

The similar condensation involving tertiary amyl bromide and ethylene in the presence of ferric chloride and bismuth trichloride yielded the bromoheptane, 1-bromo-3,3 -dimethy1pentane.

EXAMPLE XVIII A large scale run Was made at superatmospheric pressure in an autoclave equipped with a very efiicient stirrer, this equipment being gen erally referred to as a turbomixer. 34 grams of anhydrous ferric chloride was placed in the turbomixer which was then sealed, cooled to '7 8 C., and evacuated. To the evacuated turbomixer containing the ferric chloride, 680 grams of tertiary butyl chloride was introduced, operation of the stirrer was started, ethylene was added to a pressure of 2'7 atmospheres, and the temperature was permitted to rise to l C. at which rapid absorption of ethylene occurred. Within l6 XV was charged with 50 grams of tertiary butyl chloride, grams of propylene and '7 grams of titanium tetrachloride. Nitrogen was then introduced to the autoclave to a pressure of 50 atmospheres and the autoclave was rotated and heated at 50 C. for a period of 4 hours. After the autoclave and contents had cooled to room temperature, 72 grams of a liquid product and 6 grams of brown catalyst sludge were removed therefrom. Distillation of the liquid product removed therefrom 21 g. of a chloroheptane boiling between 138 and 146 C. and having a refractive index of 1.428. In addition to the chlorohep tane, some higher boiling products also resulted. The titanium tetrachloride catalyst employed was soluble in the liquid reactants but during the reaction it was converted into a brown sludge.

EXAMPLE XX Several runs were made in which tertiary butyl chloride was condensed with 1-butylene and 2- butylene in the presence of ferric chloride or bismuth trichloride. The operating temperatures used, the amounts of the different reactants, and the results obtained are summarized in Table '7.

Table 7 .-C0,ndensation of tertiary butyl chloride with i-butylene and Z-butylene in the presence of ferric chloride and bismuth chloride Main Product, B C H CsHn Run No. g gg (3,.Hz,1 Catalyst grams Temp., 0.

grams g gfi 84 1-04Hs FGCl3 4 20 T20 10 50 39 668 2O4Ha 405 .(10 11 120 10 453 42 150 2C4HE 76 "11011.. 5 130 65 439 l.C4Ha 242 BiCla. 51 +20 220 1 35 9O 2-C Ha ...d0.... 18 +25 28 24 1 At least 80% of the theoretical based on the converted t-butyl chloride.

1 minute after the reaction began, the pressure had decreased to 1 atmosphere and the temperature reached 8 C. The cooling bath was again placed around the turbomixer and ethylene was recharged thereto to 1.7 atmospheres. Reaction was rapid and the pressure decreased to 1 atmosphere Within 1 minute. The turbomixer was thus recharged intermittently with ethylene over a period of 1 hour during which the reaction temperature was maintained between 5 and +5 C. At the end of this time, absorption of ethylene was slow, even when the ethylene pressure was increased to 7.8 atmospheres. Then the stirring was stopped and 810 grams of liquid product was discharged from the turbomixer. The used catalyst was a brown solid wetted with liquid product. The liquid product which was recovered from the turbomixer after washing, drying, and distilling, yielded 490 grams of 1-chloro-3,3- dimethylbutane and 30 grams of 1-chloro-3,3 dimethylpentane, these amounts representing yields of 55 and 6% respectively, based upon the amount of tertiary butyl chloride charged.

EXAMPLE XIX An autoclave as described in Examples X to Runs Nos. 17 and 18 were carried out in a cylindrical glass reactor at atmospheric pressure. Run No. 19 was made using the procedure of Example XVI, while run Nos. 20 and 21 were carried out following the procedure of Example XII.

In run 19, the condensation was carried out in a solvent, that is 50 grams of n-pentane was also present in the reaction mixture. In this run, a 65% yield of 2-chloro-3,4,4-trimethylpentane was obtained by passing the Z-butylene into a well-stirred mixture of tertiary butyl chloride, n-pentane, and ferric chloride at -30 C. and at atmospheric pressure. In another run made in the presence of bismuth trichloride as catalyst, little or no condensation occurred at 10 C. but a 24% yield of the desired chloro-octane was obtained as shown in Table '7 when the reaction was carried out in a rotating autoclave at 25 C.

The chloro-octane obtained by the condensation of tertiary butyl chloride with l-butylene consisted of 3-chloro-5,5-dimethylhexane; that obtained by the reaction of tertiary butyl chloride with Z-butylene consisted largely of 2-chloro- 3,4,4-trimethylpentane. The physical properties of these chlorooctanes are listed in Table 8.

Tobie agents-cal propertie of thc'hio rb-ecftones obtained by the reacti n of r-bntyz chloride with 1=butyzene and z-butyzeae' From t-butyl chloride and l-Butylene 2-iiutylene Run No 17 20 1 21 (iatalyst FeCla BiCla Fel: BiCls l mm I 153 156 160-160 155F160 Refractive Index, no i 1. 4300 1.4435 1.4430 DBilSity, d4 '0. 9031 Molecular R cf r am i on (Called. for CeHnGl, v e 43.85 '43; 9 9 43;62

The condensation of tertiary amyl chloride with 2-butylene took place very s lowly at C.

and atatmospheric pressure in the presenceof ferric chloride. Condensation took place readily at 25f C. giving a 31% yield of thechlorononane, 2-chloro-3,4,4-trimethylhexane E118 chloro nonane had the-following properties; boiling point,

72-75 C. at 16mm. or l82-l85 C. atliii) mm; "n 1.448; (14 1-09019.

The corresponding bromononane'was obtained in about a 19% yield by reacting tertiary amyl bromide and- Z-butylene at2 5" C. inthe presence of a bismuth chloride catalyst. The bromono; nane boile'cl at 53-57? 6. at-3 mm; pressure' i'l93 to 197" C. at atmospheric pressure); @52 1. 168.

A mixture'of 11o grams'of tertiary amyl only ride, 42 grams of propylene, and 5 grams of-ferric chloride Wasplaced in a rotatable steel auto clave and rotated therein at 25 for 4 hours after which the autoclave and contents stood at room'temperature for about hours. The r'eac tion mixture so obtained consisted of 132 grams of a dark red liquid containing brown catalyst particles as well as gramsof unconverted .propylene. The dark'red liquid upon being washed, dried; and distilled yielded 15 g. of a chloro=octane boiling at 157-162" C.

v EXAMPLE XXIV The "autoclave employed in Exammes to XV, inclusive, was chargedwith 38 grams "of tertiary butyl iodide, 15 grams or propylene and'r r'ams offerric chloride, and then the contents of the autoclave were placed under a nitrogen pressure of E'Oatmospheres: The autoclave was th'en'rotated at 31 C. for 4 hours. The reaction product so obtained contained 22 grams of iodoheptan'e boiling at 60-66 C. at a pressure 'of 20-'-22'in'm'. of mercury. lThi's iodoheptane was mainly- 2- i'odo i,e oimetnymentane'.

estate Z. i EXAMPLE XXV Several runs were made on the condensation of monohaloalkanes with monoolefins in the presence of solutions of -a Friedel-Crafts type catalyst in a solvent such as a nitroparafiin or ether. With the bismuth chloride catalyst in n-itromethane solution, condensation of tertiary butyl' chloride and propylene tookplace atabout C., yielding chloroheptane together with some unsaturated products, possibly polymers of propylene or butylene. K I p a A nitrometha-ne solution oi ferric chloride cata lyzed the condensation of tertiary butyl chloride with ethylene at 23 C.-, yielding c hlorohexane as the chie f product. A V y V The condensation of tertiary butyl chloride with propylene was catalyzed by bismuth chloride in ethyl ether solution at a reaction temperature of 60 C. I ;A good y-ieldoi chloroheptane was obtained when tertiary butyl chloride and propylenewere treated with a solution of aluminum chloride in ethyl ether at 59 C. and at an initial nitrogen pressure of 50 atmospheres. 'Thechlorohep tane formed had a boiling point of 1'34 -l36 C. p H lT he results obtained-in the above-described runs using different solvents are summarized in Table 9. v Table 9. -Condensatton of t-but'yl chloride with mo'no olefins in the presence of nitrom'ethrme Z-nitmpmpam and ether Temp. 6

Olefin, v

eirthy'iene char es" to 50-55 an e Ethylene "charged to 40mm.

In a rotatable steel autoclave at about 25 G.- and at atmospheres pressure, t-butyl chlo: ride reacted with propylene in the presence of; anhydrous zinc chloride yielding chloroheptane n 20%. ie l lrb se Qn., h ri charged. At 5Q" C. a 30% yield oi chlorohep fame was obtained similarly in the presence of a- 1 catalyst consisting of 25% zinc chloride and 7 of alumina. latter yi'eld oi chioroheptane was based upon the t-buty l chloride which. reacted. w n W I i l he ch'loroheptane obtained in the presence: of the alumina-containing catalyst seemed to; have a wider boiling range than did" the product; Obtained with pure zinc chloride.

EXAMPLE XXVII leog'rarnsof 't-b'utyl chloride, 81 grainsor proyiene, 1"0 grams or bismuth chloride; and" 1b" grains of alumina powder were placed in a glass? lin'ed steel autoclave androtate'd at. 25 c. timeofrour hours. 755 grams or nouidproductf obtained from three or such runs was"wa"shed dried, and distilled." A total or 290" grainis'" of 19 chloroheptane was obtained consisting of two isomers, one boiling at 129-130 C. and the other at about 136-138 C.

EXANIPLE XXVIII 9 grams of heptyl bromide boiling from 148 to 153 C. was obtained by contacting 42 grams of t-butyl bromide, 21 grams of propylene, and grams of mercuric chloride in a glass-lined rotating autoclave at 40 0., for 4 hours. tially the same result was obtained on treating a similar reaction mixture at 60 C.

The character of the invention and type of results obtained by its use are evident from the preceding specification and examples although neither section should be construed to impose undue limitations upon the broad scope of the invention.

I claim as my invention:

1. A process which comprises reacting a monohaloalkane having at least three carbon atoms per molecule and a halogen of at least 35 atomic weight with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monohaloalkane having a molecular weight equal to the sum of the molecular weights of the reacting monohaloalkane and monoolefin.

2. A process which comprises reacting a monochloroalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst and at a temperature such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

3. A process which comprises reacting a monobromoalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monobromoalkane and monoolefin.

4. A process which comprises reacting a monoiodoalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monoiodoalkane having a molecular weight equal to the sum of the molecular weights of the reacting monoiodoalkane and monoolefin.

5. A process which comprises reacting a monochloroalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of aluminum chloride at a temperature of from about 30 to about 10 C. such that the principal reaction of 10 Essenthe process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

6. A process which comprises reacting a monochloroalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which atleast one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of ferric chloride at a temperature of from about 0 to about 50 C. such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

7. A process which comprises reacting a mono chloroalkane having at least three carbon atoms per molecule with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of bismuth trichloride at a temperature of from about to about 100 C. such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

8. The process of claim 1 further characterized in that the first-mentioned monohaloalkane is a primary alkyl halide.

9. The process of claim 1 further characterized in that the first-mentioned monohaloalkane is a secondary alkyl halide.

l0. ihe process of claim 1 further characterized in that the first-mentioned monohaloalkane is a tertiary alkyl halide.

11. A process which comprises reacting isopropylchloride with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloralkane and monoolefin.

12. A process which comprises reacting tertiary butyl chloride with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel-Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

13. A process which comprises reacting a primary butyl chloride with an aliphatic monoolefin in which at least one hydrogen atom is combined with each of the carbon atoms joined by the double bond in the presence of a Friedel- Crafts metal halide catalyst at a temperature such that the principal reaction of the process is the formation of a monochloroalkane having a molecular weight equal to the sum of the molecular weights of the reacting monochloroalkane and monoolefin.

14. The process of claim 1 further characterized in that the first mentioned monohaloalkane is a primary alkyl halide and said aliphatic monoolefin is ethylene.

15. The process of claim 1 further characterized in that the first-mentioned monohaloalkane;

21 22 is a secondary alkyl halide and. said aliphatic Number Name Date monoolefin is ethylene. 2,297,564 Kirkbride Sept. 29, 1942 16. The process of claim 1 further character- 2,419,500 Peterson et a1 Apr. 22, 1947 ized in that the first-mentioned monohaloalkane is a tertiary alkyl halide and said. alliphatic mono- 5 FOREIGN PATENTS olefin is ethylene. Number Country Date 17. The process of claim 5 further character- 261,539 Germany July 2, 1913 ized in that said aliphatic monoolefin is ethylene. 595,125 a e Dec. 11, 1930 LOUIS SCHMERLING. 324,909 ran Feb. 18, 1938 OTHER REFERENCES REFERENCES CITED S h r The following references are of record in the paggs q l h g; Chem file of this patent:

UNITED STATES PATENTS Number Name Date 2,068,772 Sixt Jan. 26, 1937 

1. A PROCESS WHICH COMPRISES REACTING A MONOHALOCLAKANE HAVING AT LEAST THREE CARBON ATOMS PER MOLECULE AND A HALOGEN OF AT LEAST 35 ATOMIC WEIGHT WITH AN ALIPHATIC MONOOLEFIN IN WHICH AT LEAST ONE HYDROGEN ATOM IS COMBINED WITH EACH OF THE CARBON ATOMS JOINED BY THE DOUBLE BOND IN THE PRESENCE OF A FRIEDEL-CRAFTS METAL HALIDE CATALYST AT A TEMPERATURE SUCH THAT THE PRINCIPAL REACTION OF THE PROCESS IS THE FORMATION OF A MONOHALOALKANE HAVING A MOLECULAR WEIGHT EQUAL TO THE SUM OF THE MOLECULAR WEIGHTS OF THE REACTING MONOHALOALKANE AND MONOOLEFIN. 